Low-temperature deposition process for forming molybdenum-based materials with improved resistivity

Abstract

This method includes performing a reactant step of the deposition cycle of a deposition process to form a molybdenum (Mo)-based material, performing a Mo precursor step of the deposition cycle, and performing a processing step of the deposition cycle. Performing the reactant step includes introducing reactants, performing the Mo precursor step includes introducing a Mo precursor, and performing the processing step includes introducing a processing gas. The deposition process is carried out at a temperature of approximately 450°C or lower.

Description

[Technical Field]

[0001]

[0001] Embodiments of the present disclosure generally relate to the manufacture of electronic devices. In particular, embodiments of the present disclosure relate to low-temperature deposition processes for forming molybdenum (Mo)-based materials with improved resistivity. [Background technology]

[0002]

[0002] An electronic device manufacturing apparatus may include a plurality of chambers, such as a processing chamber and a load lock chamber. Such an electronic device manufacturing apparatus may use a robotic device in a transfer chamber configured to transfer substrates between the plurality of chambers. In some cases, multiple substrates are transferred together. A processing chamber may be used in an electronic device manufacturing apparatus to perform one or more processes on a substrate, such as a deposition process and an etching process. In many processes, a gas is flowed into the processing chamber. [Overview of the Initiative]

[0003]

[0003] According to one embodiment, a method is provided. The method includes performing a reactant step of the deposition cycle of a deposition process to form a molybdenum (Mo)-based material, performing a Mo precursor step of the deposition cycle, and performing a processing step of the deposition cycle. Performing the reactant step includes introducing reactants, performing the Mo precursor step includes introducing a Mo precursor, and performing the processing step includes introducing a processing gas. The deposition process is carried out at a temperature of about 450°C or less.

[0004]

[0004] According to one embodiment, a device is provided. The system includes a trench and a liner formed along the trench, which includes a Mo-based material. The Mo-based material has a resistivity of about 200 microohms / cm (μΩ·cm) or less.

[0005]

[0005] The disclosure is shown as examples, not as limitations, in the drawings of the accompanying drawings where similar references show similar components. It should be noted that various references to “an” or “one” embodiments in the disclosure do not necessarily refer to the same embodiment, but rather to “at least one.” [Brief explanation of the drawing]

[0006] [Figure 1A-1E] This is a cross-sectional view illustrating an exemplary method for manufacturing electronic devices using a low-temperature molybdenum (Mo) based material deposition process according to several embodiments. [Figure 2] This is a flowchart illustrating an exemplary method for manufacturing electronic devices using a low-temperature process, according to several embodiments, to form molybdenum (Mo)-based materials with improved resistivity. [Figure 3] This figure illustrates an exemplary method for low-temperature molybdenum (Mo)-based material deposition according to several embodiments. [Figure 4] This figure illustrates an exemplary method for low-temperature molybdenum (Mo)-based material deposition according to several embodiments. [Figure 5] This is a top view of a multi-chamber processing platform system that may be used to carry out a low-temperature molybdenum (Mo)-based material deposition method according to several embodiments. [Modes for carrying out the invention]

[0007]

[0011] Embodiments described herein relate to low-temperature deposition processes for forming molybdenum (Mo)-based materials with improved resistivity. As the size of semiconductor technology nodes continues to shrink (e.g., to about 3 nanometer (nm) nodes or less), the electronic performance of conductive materials becomes even more critical for advanced chip performance. To further improve conductivity, the contribution of liner resistivity can be considered. Some liners are formed from materials with relatively high resistance, such as tungsten-based liners. Examples of tungsten-based liners include tungsten nitride.

[0008]

[0012] Molybdenum (Mo)-based materials can exhibit lower resistivity compared to other materials such as tungsten nitride. However, Mo has strong bonding energies with elements such as carbon (C), nitrogen (N), and oxygen (O). Therefore, achieving proper deposition of Mo-based materials from organometallic precursors can be challenging. An example of a Mo-based material is molybdenum nitride (MoN). Some processes for depositing MoN materials involve using (Mo(NR)2(NR2))2 precursors, resulting in films with higher resistivity, which may be undesirable for more advanced technology nodes. For example, MoN materials deposited using such precursors can be formed to have a thickness of about 10 nm and a corresponding resistivity exceeding about 1000 microohms / cm (μΩ·cm). In addition, some Mo-based material deposition processes can use Mo-based halides, which can damage the underlying conductive layer (e.g., a metal layer) and can be performed at high temperatures (e.g., above about 400°C), further discouraging the implementation of Mo-based liners for advanced technology nodes.

[0009]

[0013] To address these and other drawbacks, embodiments described herein provide low-temperature deposition processes for forming Mo-based materials with improved resistivity. For example, Mo-based materials can be formed on a dielectric material. In some embodiments, the dielectric material includes silicon dioxide (SiO2) (i.e., silica). Additionally or alternatively, Mo-based materials can be formed on conductive materials such as metals or titanium nitride (TiN) liners. In some embodiments, the Mo-based material includes molybdenum nitride (MoN). In some embodiments, a Mo-based material having a thickness of about 10 nm or less is formed. In some embodiments, the Mo-based material has a resistivity of about 200 μΩ·cm or less. In some embodiments, the resistivity of the Mo-based material ranges from about 50 μΩ·cm to about 200 μΩ·cm. Thus, Mo-based materials formed according to embodiments described herein may have lower resistivity compared, for example, tungsten nitride.

[0010]

[0014] The deposition process allows for conformal deposition of Mo-based materials on a surface. In some embodiments, the deposition process is chemical vapor deposition (CVD). In some embodiments, the deposition process is atomic layer deposition (ALD).

[0011]

[0015] The deposition process described herein may comprise several deposition cycles. Each deposition cycle comprises a reactant step for introducing reactants, a Mo precursor step for introducing a Mo precursor, and a processing step for introducing a processing gas. A first purging step may be performed between the reactant step and the Mo precursor step, a second purging step may be performed between the Mo precursor step and the processing step, and a third purging step may be performed after the processing step. More specifically, each purging step may include the introduction of a purging gas and have an associated purging time. A longer purging time in at least the first purging step can improve the uniformity of conformal deposition of the Mo-based material. The purging gas may include any suitable inert or non-reactive gas (e.g., a noble gas). For example, the purging gas may include a noble gas (e.g., argon (Ar)), nitrogen gas (N2), etc. In some embodiments, each purging step has a purging gas pulse time between about 0.5 seconds and about 50 seconds. In some embodiments, each purge step has a purge gas pulse time between about 1 second and about 10 seconds.

[0012]

[0016] In some embodiments, the number of deposition cycles ranges from about 1 to about 200 cycles. In some embodiments, the number of deposition cycles ranges from about 5 to about 150 cycles. In some embodiments, the number of deposition cycles ranges from about 10 to about 100 cycles. In some embodiments, the deposition process is carried out at a temperature of about 450°C or less. In some embodiments, the deposition process is carried out at a temperature in the range of about 200°C to about 450°C. In some embodiments, the deposition process is carried out at a temperature in the range of about 250°C to about 400°C. In some embodiments, the deposition process is carried out at a temperature in the range of about 300°C to about 375°C. In some embodiments, the deposition process is carried out at a pressure in the range of about 0.5 torr to about 300 torr. In some embodiments, the deposition process is carried out at a pressure in the range of about 2 torr to about 100 torr. In some embodiments, the deposition process is carried out at a pressure in the range of about 2 torr to about 50 torr.

[0013]

[0017] More specifically, during the reactant step, reactants are introduced to cleave the Mo-C bond of the ligand for depositing the Mo-based material without an excit-to reducing source (e.g., excit-to hydrogen source) and with little or no damage to the underlying conductive layer (e.g., metal layer). The reactant step may have an associated reaction pulse time. In some embodiments, the reaction pulse time ranges from about 0.1 second to about 5 seconds. In some embodiments, the reaction pulse time ranges from about 0.2 second to about 1 second.

[0014]

[0018] The reactant may be represented by the formula RX y where X is a halogen (e.g., chlorine (Cl), bromine (Br), or iodine (I)), and y = 1 or y = 2. For example, when y = 1, R may be an alkyl group having the chemical formula C n H 2n+1 where 1 ≤ n ≤ 10. Thus, in some embodiments, the reactant includes a halogenated alkyl (i.e., haloalkane or halogenoalkane). Generally, a halogenated alkyl is an alkane containing a halogen substituent. For example, a halogenated alkyl can be formed from an alkane having the chemical formula C n H 2n+2 through halogenation (e.g., chlorination, bromination, or iodination). Examples of halogenated alkyls include methyl halide, ethyl halide, and the like.

[0015]

[0019] As another example, when y = 2, R may be an alkylene group having the chemical formula C n H 2n where 1 ≤ n ≤ 10. Thus, in some embodiments, the reactant includes an alkylene dihalide (i.e., haloalkene or halogenoalkene). Generally, an alkylene dihalide is an alkene containing a halogen substituent. For example, an alkylene dihalide has the chemical formula C n H 2nIt can be formed from an alkene having via halogenation. Examples of the dihalogenated alkylene include methylene dihalides, ethylene dihalides, and the like.

[0016]

[0020] Exemplarily, when the reactant includes an alkyl halide, the beta hydride elimination can provide an in situ reducing source that transfers hydrogen from the alkyl group or alkylene group to Mo. This enables the reduction of Mo and the ability of the alkyl group to leave the Mo surface as an alkene. In some embodiments, the reactant is an iodine-containing reactant. For example, the reactant can include an alkyl iodide or an alkylene iodide. The general mechanism of the iodine-containing reactant substance is that it can decompose on the metal surface to form a metal iodide. Iodine induces the cleavage of the Mo-C bond to form Mo-I having a ligand removed from the Mo atom.

[0017]

[0021] During the Mo precursor step, the Mo precursor is introduced. The Mo precursor step can have an associated Mo precursor pulse time. In some embodiments, the Mo precursor pulse time ranges from about 0.2 seconds to about 5 seconds. In some embodiments, the Mo precursor pulse time ranges from about 1 second to about 4 seconds. In some embodiments, the Mo precursor includes a Mo-based amide. Examples of the Mo precursor include Mo(imide)2(amino)2, Mo(amino)4, bis(benzene)molybdenum, bis(ethylbenzene)molybdenum, bis(trimethylsilyl)benzene molybdenum, bis(propyl)benzene molybdenum, bis(isopropyl)benzene molybdenum, alkyl-substituted benzene, and the like. The alkyl on the benzene can have 0 to 5 carbons. The alkyl on the benzene can be a mono-, di-, or tri-substituted benzene.

[0018]

[0022] During the processing step, a processing gas is introduced to improve the quality of the Mo-based material. For example, the processing gas may increase the adhesion of the Mo-based material to a dielectric material (e.g., SiO2 and / or silicon nitride). As another example, the processing gas may improve the smoothness of the Mo-based material. For example, the smoothness of the Mo-based material may be about 0.2 nm at a thickness of about 20 nm. The processing step may have a processing gas pulse time. In some embodiments, the processing gas pulse time is in the range of about 1 second to about 150 seconds. In some embodiments, the processing gas pulse time is in the range of about 50 seconds to about 150 seconds. The processing gas may include any suitable gas. In some embodiments, the processing gas includes ammonia gas (NH3). In some embodiments, the flow rate of the processing gas is in the range of about 10 standard cubic centimeters / minute (sccm) to about 5000 sccm. In some embodiments, the flow rate of the processing gas is in the range of about 250 sccm to about 2000 sccm. In some embodiments, the flow rate of the process gas is in the range of about 400 sccm to about 1000 sccm.

[0019]

[0023] In some embodiments, the deposition processes described herein are used to form a liner during the manufacture of electronic devices. For example, at least one via opening can be formed within an interlevel dielectric (ILD) layer placed on a substrate, so that a portion of the ILD layer is separated by the via opening. Mo-based material can be conformally deposited as a liner along the exposed surface of the ILD layer portion, including the sidewalls of the via opening. A conductive material (e.g., a metal) can then be formed on the liner within the via opening. Additionally or alternatively, Mo-based material can be deposited on a conductive liner (e.g., a metal liner) during logic or memory integration. Further details regarding the formation of Mo-based materials with improved resistivity are described below with reference to Figures 1A to 5.

[0020]

[0024] Figures 1A to 1E are cross-sectional views illustrating exemplary methods for forming an electronic device ("device") 100 according to several embodiments. As shown in Figure 1A, the device 100 may include a substrate 110. In some embodiments, the substrate 110 includes a substrate layer corresponding to the initial layer of the device 100 (e.g., a semiconductor wafer). For example, the substrate layer may include silicon (Si).

[0021]

[0025] Figure 1B shows the formation of the ILD layer 120 on the substrate 110. The ILD layer 120 may contain any suitable dielectric material. In some configurations, the ILD layer 120 contains an oxide (e.g., a metal oxide). Examples of suitable dielectric materials include SiO2, carbon-doped silicon oxide (e.g., SiOC, SiCOH), etc.

[0022]

[0026] Figure 1C shows the formation of at least one via opening 130 within the ILD layer 120, resulting in ILD layer portions 125-1 and 125-2. The at least one via opening 130 can be formed using any suitable via patterning process according to the embodiments described herein.

[0023]

[0027] Figure 1D shows the formation of a liner 140 along the exposed surfaces of ILD layer portions 125-1 and 125-2, including the sidewall of at least one via opening 130. Additionally or alternatively, the liner 140 is formed on a conductive material such as a metal or TiN liner. More specifically, the liner 140 may include a Mo-based material. In some embodiments, the Mo-based material is MoN. The liner 140 may be formed using a deposition process to form the Mo-based material. In some embodiments, the deposition process is an ALD process. In some embodiments, the deposition process is a CVD process. In some embodiments, the liner 140 formed using a deposition process has a thickness of about 10 nm or less. In some embodiments, the liner 140 formed using a deposition process has a resistivity of about 200 μΩ·cm or less. In some embodiments, the resistivity of the liner 140 is in the range of about 50 μΩ·cm to about 200 μΩ·cm.

[0024]

[0028] The deposition process described herein may comprise several deposition cycles. Each deposition cycle comprises a reactant step for introducing reactants, a Mo precursor step for introducing a Mo precursor, and a processing step for introducing a processing gas. A first purging step may be performed between the reactant step and the Mo precursor step, a second purging step may be performed between the Mo precursor step and the processing step, and a third purging step may be performed after the processing step. More specifically, each purging step may include the introduction of a purging gas and have an associated purging time. A longer purging time in at least the first purging step can improve the uniformity of conformal deposition of the Mo-based material. The purging gas may include any suitable inert or non-reactive gas (e.g., a noble gas). For example, the purging gas may include a noble gas (e.g., Ar), N2, etc. In some embodiments, each purging step has a purging gas pulse time between about 0.5 seconds and about 50 seconds. In some embodiments, each purging step has a purging gas pulse time between about 1 second and about 10 seconds.

[0025]

[0029] In some embodiments, the number of deposition cycles ranges from about 1 to about 200 cycles. In some embodiments, the number of deposition cycles ranges from about 5 to about 150 cycles. In some embodiments, the number of deposition cycles ranges from about 10 to about 100 cycles. In some embodiments, the deposition process is carried out at a temperature of about 450°C or less. In some embodiments, the deposition process is carried out at a temperature in the range of about 200°C to about 450°C. In some embodiments, the deposition process is carried out at a temperature in the range of about 250°C to about 400°C. In some embodiments, the deposition process is carried out at a temperature in the range of about 300°C to about 375°C. In some embodiments, the deposition process is carried out at a pressure in the range of about 0.5 torr to about 300 torr. In some embodiments, the deposition process is carried out at a pressure in the range of about 2 torr to about 100 torr. In some embodiments, the deposition process is carried out at a pressure in the range of about 2 torr to about 50 torr.

[0026]

[0030] More specifically, during the reactant step, reactants are introduced to break the Mo-C bonds of ligands for depositing Mo-based materials without an excite reduction source (e.g., an excite hydrogen source) and with little to no damage to the underlying conductive layer (e.g., a metal layer). The reactant step may have a corresponding reaction pulse time. In some embodiments, the reaction pulse time is in the range of about 0.1 seconds to about 5 seconds. In some embodiments, the reaction pulse time is in the range of about 0.2 seconds to about 1 second.

[0027]

[0031] The reactants are, formula RX y It can be expressed as follows: where X is a halogen (e.g., chlorine (Cl), bromine (Br), or iodine (I)) and y=1 or y=2. For example, when y=1, R is a compound of the chemical formula C n H 2n+1It can be an alkyl group having , where 1 ≤ n ≤ 10. Therefore, in some embodiments, the reactants include an alkyl halide (i.e., a haloalkane or halogenoalkane). Generally, alkyl halides are alkanes containing halogen substituents. For example, via halogenation (e.g., chlorination, bromide or iodization), the chemical formula C n H 2n+2 Alkyl halides can be formed from alkanes containing [a specific compound]. Examples of alkyl halides include methyl halides and ethyl halides.

[0028]

[0032] As another example, when y=2, R is the chemical formula C n H 2n It may be an alkylene group having , where 1 ≤ n ≤ 10. Therefore, in some embodiments, the reactants include a dihalogenated alkylene (i.e., a haloalkene or halogenoalkene). Generally, dihalogenated alkylenes are alkenes containing halogen substituents. For example, a dihalogenated alkylene has the chemical formula C n H 2n They can be formed from alkenes containing [a specific compound] via halogenation. Examples of dihalogenated alkylenes include dihalogenated methylene, dihalogenated ethylene, and trishalides.

[0029]

[0033] For example, if the reactants contain an alkyl halide, the removal of the beta-hydride can provide an in-situ reduction source for transferring hydrogen from the alkyl group to Mo. This enables a reduction in Mo and the ability of the alkyl group to leave the Mo surface as an alkene.

[0030]

[0034] In some embodiments, the reactants are iodine-containing reactants. For example, the reactants may include alkyl iodides or alkylene iodides. A common mechanism of iodine-containing reactants is that they can decompose on a metal surface to produce metal iodides. Iodine induces the cleavage of the Mo-C bond, forming Mo-I with ligands removed from the Mo atoms.

[0031]

[0035] During the Mo precursor step, the Mo precursor is introduced. The Mo precursor step may have a corresponding Mo precursor pulse time. In some embodiments, the Mo precursor pulse time is in the range of about 0.2 seconds to about 5 seconds. In some embodiments, the Mo precursor pulse time is in the range of about 1 second to about 4 seconds. In some embodiments, the Mo precursor includes a Mo-based amide. Examples of Mo precursors include Mo(imide)2(amino)2, Mo(amino)4, bis(benzene)molybdenum, bis(ethylbenzene)molybdenum, bis(trimethylsilyl)benzenemolybdenum, bis(propyl)benzenemolybdenum, bis(isopropyl)benzenemolybdenum, alkyl-substituted benzene, etc. The alkyl on the benzene may be 0 to 5 carbon atoms. The alkyl on the benzene may be mono, di, or tri-substituted benzene.

[0032]

[0036] During the processing step, a processing gas is introduced to improve the quality of the Mo-based material. For example, the processing gas may increase the adhesion of the Mo-based material to a dielectric material (e.g., SiO2 and / or silicon nitride). As another example, the processing gas may improve the smoothness of the Mo-based material. For example, the smoothness of the Mo-based material may be about 0.2 nm at a thickness of about 20 nm. The processing step may have a processing gas pulse time. In some embodiments, the processing gas pulse time is in the range of about 1 second to about 150 seconds. In some embodiments, the processing gas pulse time is in the range of about 50 seconds to about 150 seconds. The processing gas may include any suitable gas. In some embodiments, the processing gas includes ammonia gas (NH3). In some embodiments, the flow rate of the processing gas is in the range of about 10 sccm to about 5000 sccm. In some embodiments, the flow rate of the processing gas is in the range of about 250 sccm to about 2000 sccm. In some embodiments, the flow rate of the process gas is in the range of about 400 sccm to about 1000 sccm.

[0033]

[0037] Figure 1E shows the formation of the conductive material 150 on the liner 140 and within at least one via opening 130. For example, the conductive material 150 can form vias within at least one via opening 130, conductive lines formed on the vias, and portions of the liner 140 positioned on the upper surfaces of ILD layer portions 125-1 and 125-2. The conductive material 150 may include any suitable material (e.g., a metal). In some embodiments, the conductive material 150 includes a transition metal. Examples of suitable materials that may be used to form the conductive material 150 include Cu, W, Co, Mo, Ru, TiN, TaN, and MoN. x These are some of the features included. Further details regarding the manufacturing device 100 will be described later with reference to Figure 2.

[0034]

[0038] Figure 2 shows an exemplary method 200 for manufacturing electronic devices using region-selective deposition, according to several embodiments. Method 200 can be performed within an electronic device processing system. More specifically, Method 200 can be performed within one or more processing chambers of an electronic device processing system. An exemplary electronic device processing system is described below with reference to Figure 5.

[0035]

[0039] Step 210 provides a base structure for an electronic device. In some embodiments, the base structure includes a substrate, an ILD layer disposed on the substrate, and at least one via opening through the ILD layer. The substrate may include at least a substrate layer (e.g., a Si substrate). The substrate may further include one or more additional layers. The ILD layer may include any suitable dielectric material. In some embodiments, the ILD layer includes a silicate. For example, the ILD layer may include SiO2.

[0036]

[0040] In some embodiments, obtaining a base structure includes receiving a preformed base structure. In some embodiments, obtaining a base structure includes forming at least a portion of a base structure. For example, forming at least a portion of a base structure may include at least one of forming an ILD layer on a substrate (e.g., directly on a substrate layer or one or more additional layers) or forming at least one opening through the ILD layer to form at least two ILD layer portions separated by at least one opening.

[0037]

[0041] Forming at least one opening may include forming at least one trench within the ILD layer. For example, forming at least one trench may include performing an etching process. If the base structure does not include a dielectric cap containing an etching stop layer formed on the ILD layer, then at least one trench may be equal to at least one opening. Alternatively, if the base structure further includes a dielectric cap disposed on the ILD layer, then trench formation using an etching process may stop at the etching stop layer. Thus, forming at least one opening may further include performing an additional etching process (e.g., an anisotropic etching process) to remove the dielectric cap. In some embodiments, at least one opening is a via opening. In some embodiments, at least one opening is formed by perforating through the ILD layer.

[0038]

[0042] In step 220, a liner is formed on the base structure to obtain an intermediate structure. Forming the liner may involve conformally depositing the liner material along the exposed surfaces of at least two ILD layer portions. For example, the liner material may be conformally deposited along the sidewall of at least one opening and along the upper surfaces of at least two ILD layer portions. In some embodiments, the liner material includes a Mo-based material. In some embodiments, the liner is formed to have a thickness of about 10 nm or less. In some embodiments, the liner is formed to have a thickness of about 3 nm or less. In some embodiments, the liner has a resistivity of about 200 μΩ·cm or less. In some embodiments, the resistivity of the liner is in the range of about 50 μΩ·cm to about 200 μΩ·cm. Further details regarding forming the liner on the base structure are described above with reference to Figure 1 and further described below with reference to Figures 3-4.

[0039]

[0043] In step 230, additional processing is performed on the intermediate structure to obtain a final structure corresponding to the electronic device. Performing additional processing may include forming a conductive material on the liner. For example, forming a conductive material on the intermediate structure may include forming a first portion of the conductive material in at least one opening and forming a second portion of the conductive material on the liner portion formed on the upper surface of the first portion of the conductive material and the ILD layer portion. In some embodiments, the first portion of the conductive material corresponds to at least one via, and the second portion of the conductive material corresponds to a conductive wire. The conductive material may include any suitable material (e.g., metal). Examples of suitable materials that may be used to form the conductive material include Cu, W, Co, Mo, Ru, TiN, TaN, and MoN. x This includes the above. Further details regarding steps 210-230 are described above with reference to Figures 1A-1E, and will be described later with reference to Figures 3-4.

[0040]

[0044] Figure 3 is a flowchart illustrating exemplary method 300 for low-temperature Mo-based material deposition according to several embodiments. For example, method 300 can be performed in one or more processing chambers of an electronic device processing system. For example, one or more processing chambers may include one or more CVD chambers and / or one or more ALD chambers. In some embodiments, method 300 is performed during step 220 of Figure 2 to form a liner containing Mo-based material on a base structure in order to obtain an intermediate structure during the manufacture of an electronic device. For example, the liner may be formed in a trench during via formation.

[0041]

[0045] Step 310 is performed, which is the reactant step of the deposition cycle of the deposition process. The deposition process can conformally deposit a Mo-based material onto a surface. In some embodiments, the surface is a dielectric material. For example, the dielectric material may be a silicate (e.g., SiO2). In some embodiments, the dielectric material corresponds to an ILD layer. In some embodiments, the deposition process is a CVD process. In some embodiments, the deposition process is an ALD process. In some embodiments, the deposition process is performed at a temperature in the range of about 200°C to about 450°C. In some embodiments, the deposition process is performed at a temperature in the range of about 250°C to about 400°C. In some embodiments, the deposition process is performed at a temperature in the range of about 325°C to about 375°C. In some embodiments, the deposition process is performed at a pressure in the range of about 0.5 torr to about 300 torr. In some embodiments, the deposition process is performed at a pressure in the range of about 2 torr to about 100 torr. In some embodiments, the deposition process is carried out at a pressure ranging from about 2 torr to about 50 torr.

[0042]

[0046] Performing the reactant step involves introducing reactants. The reactants are introduced to break the Mo-C bonds of ligands for depositing Mo-based materials without using an excite reduction source (e.g., an excite hydrogen source) and with little to no damage to the underlying conductive layer (e.g., a metal layer). The reactant step may have a corresponding reaction pulse time. In some embodiments, the reaction pulse time ranges from about 0.1 seconds to about 5 seconds. In some embodiments, the reaction pulse time ranges from about 0.2 seconds to about 1 second. Examples of reactants are described above with reference to Figures 1 and 2.

[0043]

[0047] In some embodiments, performing the reactant step further includes performing a first purge step after introducing the reactants. More specifically, the first purge step may include introducing a first purge gas. The first purge gas may include any suitable inert or nonreactive gas (e.g., a noble gas). For example, the first purge gas may include Ar. In some embodiments, the first purge step has a purge gas pulse time between about 0.5 seconds and about 50 seconds. In some embodiments, the first purge step has a purge gas pulse time between about 1 second and about 10 seconds. A longer purge time in the first purge step can improve the uniformity of conformal deposition of Mo-based materials.

[0044]

[0048] Step 320 is performed, which is the Mo precursor step of the deposition cycle. Performing the Mo precursor step involves introducing a Mo precursor. The Mo precursor step may have a corresponding Mo precursor pulse time. In some embodiments, the Mo precursor pulse time is in the range of about 0.2 seconds to about 5 seconds. In some embodiments, the Mo precursor pulse time is in the range of about 1 second to about 4 seconds. The Mo precursor may include any suitable precursor. In some embodiments, the Mo precursor includes a Mo-based amide. Examples of Mo precursors include Mo(imide)2(amino)2, Mo(amino)4, bis(benzene)molybdenum, bis(ethylbenzene)molybdenum, bis(trimethylsilyl)benzenemolybdenum, bis(propyl)benzenemolybdenum, bis(isopropyl)benzenemolybdenum, etc.

[0045]

[0049] In some embodiments, performing the Mo precursor step further includes performing a second purge step after introducing the Mo precursor. More specifically, the second purge step may include introducing a second purge gas. The second purge gas may include any suitable inert or nonreactive gas (e.g., a noble gas). For example, the second purge gas may include Ar. In some embodiments, the second purge step has a purge gas pulse time between about 0.5 seconds and about 50 seconds. In some embodiments, the second purge step has a purge gas pulse time between about 1 second and about 10 seconds.

[0046]

[0050] Step 330 performs a processing step of the deposition cycle. Performing the processing step includes introducing a processing gas. The processing step can be performed to improve the quality of the Mo-based material. For example, the processing gas may increase the adhesion of the Mo-based material to a dielectric material (e.g., SiO2 and / or silicon nitride). As another example, the processing gas may improve the smoothness of the Mo-based material. For example, the smoothness of the Mo-based material may be about 0.2 nm at a thickness of about 20 nm. The processing step may have a corresponding processing gas pulse time. In some embodiments, the processing gas pulse time is in the range of about 1 second to about 150 seconds. In some embodiments, the processing gas pulse time is in the range of about 50 seconds to about 150 seconds. The processing gas may include any suitable gas. In some embodiments, the processing gas includes NH3. In some embodiments, the flow rate of the processing gas is in the range of about 10 sccm to about 5000 sccm. In some embodiments, the flow rate of the processing gas is in the range of about 250 sccm to about 2000 sccm. In some embodiments, the flow rate of the process gas is in the range of about 400 sccm to about 1000 sccm.

[0047]

[0051] In some embodiments, performing the processing step further includes performing a third purging step after introducing the Mo precursor. More specifically, the third purging step may include introducing a third purging gas. The third purging gas may include any suitable inert or nonreactive gas (e.g., a noble gas). For example, the third purging gas may include Ar. In some embodiments, the third purging step has a purging gas pulse time between about 0.5 seconds and about 50 seconds. In some embodiments, the third purging step has a purging gas pulse time between about 1 second and about 10 seconds.

[0048]

[0052] Step 340 determines whether the deposition process is complete. For example, determining whether the deposition process is complete may include determining whether the deposition cycle is the final deposition cycle of the deposition process. If the deposition process is not complete, the process can be returned to step 310 to start another deposition cycle and perform the reactant step. Otherwise, if the deposition process is complete, the deposition process for forming the Mo-based material is complete (e.g., a Mo-based liner).

[0049]

[0053] The deposition process may have any appropriate number of cycles. In some embodiments, the number of deposition cycles ranges from about 1 to about 200 cycles. In some embodiments, the number of deposition cycles ranges from about 5 to about 150 cycles. In some embodiments, the number of deposition cycles ranges from about 10 to about 100 cycles. In some embodiments, the Mo-based material is formed to have a thickness of about 10 nm or less. In some embodiments, the Mo-based material has a resistivity of about 200 μΩ·cm or less. In some embodiments, the resistivity of the Mo-based material ranges from about 50 μΩ·cm to about 200 μΩ·cm. Further details regarding steps 310 to 340 are described above with reference to Figures 1A to 2, and hereafter with reference to Figure 4.

[0050]

[0054] Figure 400 shows exemplary methods for low-temperature molybdenum (Mo)-based material deposition according to several embodiments. The method includes a reactant step 410 for introducing reactants, a purge step 420-1 following the reactant step 410, a Mo precursor step 430, a purge step 420-2 following the Mo precursor step 430, a processing step 440 for introducing a processing gas, and a purge step 420-3 following the processing step 440. Steps 410-440 collectively form a deposition cycle ("cycle") 450 of the deposition process to form a Mo-based material with improved resistivity. In some embodiments, the deposition process is an ALD process. The deposition process may have any preferred number of cycles. In some embodiments, the number of deposition cycles ranges from about 1 to about 200 cycles. In some embodiments, the number of deposition cycles ranges from about 5 to about 150 cycles. In some embodiments, the number of deposition cycles ranges from about 10 to about 100 cycles. Further details regarding steps 410-440 are described above with reference to Figures 1-3.

[0051]

[0055] Figure 5 is a top view of a multi-chamber processing platform system ("System") 35 according to several embodiments. System 35 may be used for manufacturing electronic devices such as device 100 described above with reference to Figure 1, and / or for low-temperature Mo-based material deposition methods (e.g., for manufacturing electronic devices) such as one or more of the methods 200-400 described above with reference to Figures 2-4. The deposition process may be carried out in System 500 which may have at least one ALD chamber, at least one CVD chamber, at least one physical vapor deposition (PVD) chamber, or at least one annealing chamber placed above them.

[0052]

[0056] The system 35 may include at least two transfer chambers 48, 50, at least two transfer robots 49, 51 positioned within the transfer chambers 48, 50, respectively, and a plurality of processing chambers 36, 38, 40, 41, 42, and 43. Transfer chambers 48 and 50 may be separated by a pass-through chamber 52 which may include a cooling chamber or a preheating chamber. When transfer chambers 48 and 50 operate at different pressures, the pass-through chamber 52 may also be pumped down or ventilated during substrate handling. For example, transfer chamber 48 may operate at a pressure in the range of about 100 mmTorr to about 5 Torr, e.g., about 400 mmTorr, and transfer chamber 50 may operate at about 1 × 10⁻⁶ -5 From Torr, approximately 1 × 10 -8 Within the range up to Torr, for example, approximately 1 × 10⁻⁶ -7 It can operate under Torr pressure. The processing platform system 35 can be controlled using a microprocessor controller 54.

[0053]

[0057] The transfer chamber 48 is connected to at least two degassing chambers 44, at least two load lock chambers 46, a pre-wash chamber 42, and a chamber 36 such as a CVD processing chamber or an ALD processing chamber. Substrates can be sequentially degassed and washed in the degassing chambers 44 and the pre-wash chambers 42, respectively. A transfer robot 49 can move the substrates between the degassing chambers 44 and the pre-wash chambers 42. The substrates can then be transferred into the chamber 36 for material deposition.

[0054]

[0058] The transfer chamber 50 is connected to a cluster of processing chambers 38, 40, 41, and 43. In one embodiment, chambers 38 and 40 may include CVD chambers and / or ALD chambers for material deposition. The CVD chambers may be adapted to deposit material using CVD or ALD techniques. Chambers 41 and 43 may include rapid thermal annealing (RTA) chambers and / or rapid heat treatment (RTP) chambers that can anneal substrates at low or very low pressure. Alternatively, chambers 41 and 43 may be deposition chambers capable of performing one or more of the following: CVD, ALD, annealing, in-situ deposition, etc. Substrates can be moved from the transfer chamber 48 into the transfer chamber 50 via the pass-through chamber 52. The transfer robot 51 can then move the substrates between one or more of the processing chambers 38, 40, 41, and 43 for material deposition and annealing, as required for processing.

[0055]

[0059] Although not shown, multiple vacuum pumps are arranged in fluid communication with each transfer chamber and each processing chamber to independently regulate the pressure in each chamber. The pumps can establish a vacuum gradient that increases the pressure throughout the entire apparatus from the load lock chamber to the processing chambers. In addition, one or more etching chambers may be connected to the processing platform system 35 or to a separate processing system for etching the substrate surface. For example, one or more etching chambers may include a dry etching chamber (e.g., a plasma etching chamber) and / or a wet etching chamber.

[0056]

[0060] The above description includes numerous specific details, such as examples of particular systems, components, and methods, in order to provide a full understanding of some embodiments of the disclosure. However, it will be apparent to those skilled in the art that at least some embodiments of the disclosure can be implemented without these specific details. In other circumstances, well-known components or methods are not described in detail or are presented in simple block diagram form to avoid unintentionally obscuring the disclosure. Thus, the specific details presented are illustrative only. Certain implementations may differ from these exemplary details and are still considered to be within the scope of the disclosure.

[0057]

[0061] Throughout this specification, any reference to “a certain embodiment” or “one embodiment” means that a particular feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment. Therefore, occurrences of the phrase “in a certain embodiment” or “in one embodiment” in various places throughout this specification do not necessarily all refer to the same embodiment. Furthermore, the term “or” is intended to mean inclusive “or” rather than exclusive “or.” Where the terms “about” or “approximately” are used in this specification, it is intended that the nominal values ​​presented are accurate within ±10%.

[0058]

[0062] Although the operations of the methods described herein are shown and described in a specific order, the order of the operations of each method can be changed to perform certain operations in reverse order or to perform certain operations at least partially concurrently with other operations. In another embodiment, instructions for separate operations or suboperations can be performed intermittently and / or alternately.

[0059]

[0063] It should be understood that the above description is intended to be illustrative and not limiting. Many other embodiments will become apparent to those skilled in the art upon reading and understanding the above description. Therefore, the scope of this disclosure should be determined by referring to the appended claims and together with the entire scope of equivalents to which such claims are entitled.

Claims

1. It is a method, Forming a molybdenum (Mo)-based material by performing a reactant step of the deposition cycle of a deposition process, which includes introducing reactants, and performing a reactant step, Performing the Mo precursor step of the aforementioned deposition cycle, which includes introducing a Mo precursor, Performing the processing step of the sediment cycle, which includes introducing a processing gas, A method comprising the deposition process being carried out at a temperature of approximately 450°C or less.

2. The method according to claim 1, wherein the reactant comprises an alkyl halide.

3. The method according to claim 2, wherein the reactant comprises a dihalogenated alkylene.

4. The method according to claim 1, wherein the reactant contains iodine.

5. The method according to claim 1, wherein the Mo precursor comprises a Mo-based amide.

6. The aforementioned Mo precursor is Mo (imide) ２ (amino) ２ Mo (amino) ４ The method according to claim 1, comprising at least one of bis(benzene)molybdenum, bis(ethylbenzene)molybdenum, bis(trimethylsilyl)benzene-molybdenum, bis(propyl)benzene-molybdenum, or bis(isopropyl)benzene-molybdenum.

7. The method according to claim 1, wherein the processing gas includes ammonia gas.

8. The method according to claim 1, wherein the deposition process is carried out at a temperature in the range of about 250°C to about 400°C.

9. The method according to claim 1, wherein the deposition process is carried out at a temperature in the range of about 300°C to about 375°C.

10. The method according to claim 1, wherein the reactant step has a corresponding reaction pulse time in the range of about 0.1 seconds to about 5 seconds.

11. The method according to claim 1, wherein the Mo precursor step has a corresponding Mo precursor pulse time in the range of about 1 second to about 5 seconds.

12. The method according to claim 1, wherein the processing step has a related processing gas pulse time in the range of about 50 seconds to about 150 seconds.

13. The method according to claim 1, wherein the processing gas has a relevant flow rate in the range of about 400 standard cubic centimeters / minute (sccm) to about 1000 sccm.

14. Performing the reactant step further includes performing a first purging step after introducing the reactants, Performing the Mo precursor step further includes performing a second purging step after introducing the Mo precursor, Performing the processing step further includes performing a third purging step after introducing the processing gas. The method according to claim 1.

15. The method according to claim 14, wherein the first purge step, the second purge step, and the third purge step each have a related purge gas pulse time in the range of about 1 second to about 10 seconds.

16. The method according to claim 1, wherein the Mo-based material is formed as a liner along the trench.

17. The method according to claim 1, wherein the Mo-based material includes molybdenum nitride (MoN).

18. It is a device, Trench, and Liner containing Mo-based material formed along the trench A device comprising the above, wherein the Mo-based material has a resistivity of approximately 200 microohms-centimeters (μΩ·cm) or less.

19. The device according to claim 18, wherein the Mo-based material includes molybdenum nitride (MoN).

20. The device according to claim 18, wherein the device is associated with a technology node of less than approximately 3 nanometers.

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